Electrochemical 1,2-Migration Reactions Mediated by Vitamin B12 Derivatives
Electrolyses of an alkyl halide having two ester groups and one phenyl group on the β-carbon atom have been carried out under various conditions in the presence of a catalytic amount of the hydrophobic vitamin B12. The migration of the pheny group was observed under the conditions forming a radical intermediate. The ester-migrated product was detected under the conditions forming an anionic intermediate. This is the first successful example in selecting a migrating group by electrolysis potential. A novel vitamin B12 derivative, which has phenylalanine residues on the peripheral side chains, catalyzed effectively 1,2-migration of the carboxylic ester in 1-bromo-2,2-bis(ethoxycarbonyl)propane at −1.0 V vs. Ag/AgCl under irradiation conditions.
KeywordsRadical Intermediate Alkyl Halide Migrate Group Carboxylic Ester Phenylalanine Residue
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- Y. Murakami, Y. Hisaeda, T. Ohno, H. Kohno, T. Nishioka, J. Chem. Soc., Perkin Trans. 2, 1995, 1175.Google Scholar
- 4).Y. Murakami, Y. Hisaeda, T. Tashiro, and Y. Matsuda, Chem. Lett., 1985, 1813.Google Scholar
- Y. Murakami, Y. Hisaeda, T. Tashiro, and Y. Matsuda, Chem. Lett., 1986, 555.Google Scholar